Manufacture of anthraquinone derivatives



- aminoanthraquinones which contain a sul- Patented Oct. 11, 1932 'mo ITE T ES.

ra'rlszrrr OFFICE FRANK oner: AND wILnmM wYnDHAM TATUM, or MANCHESTER, ENGLAND, ASSIGN- ons r0 IMPERIAL cnnmcnnnvnusrmns LIMITED, or LONDON, ENGLAND mmrrnc'runn or nivrimaoumoivn nnnrvn'rrvns No Drawing; Original application filed August 29, 1929, Serial No. 384,796, and in Great Britain September 18, 1928. Divided and this application filed August 9, 1929. Serial N 0. 384,795.

The 2-alkoxy derivatives of 1 -diaminoanthraquinones are important intermediates in the manufacture of dyes. Amino and diaminoanthraquinones are not usually used as "afdyes but in BritishPatent No. 211,720 certain aminoanthraquinones and derivatives of L if the same areused to dye acetyl silks. The dyes used in the process of the patent are all insoluble in water and only very sparingly, if at all, even in strong acid solutions.

suspension. 7 v

As explained in our co-pending application is a'division, we have found that Q-alkoxy derivatives of 1za-diaminoanthraquinones 7 including in this term the alkyl or aryl N- substituted derivatives of the same may be obtained with unexpected case from 1 l-diphonic group in position 2 by reacting such diaminoanthraquinone with alkali metal alkoxides. Under alkali metal alkoxides we understand the bodies which result when alkali metal is caused; to react with an aliphatic alcohol or when an aliphatic alcohol is treated with'ja concentrated aqueous lye of an alkali metal hydroxide or when a solid alkali metal hydroxide is dissolved in an aliphatic alcohol. The alkoxide used may be derived from any of the lower aliphatic alcohols, such as methyl, ethyl; propyl, isopropyl, butyl, isobutyl, tertiary butyl, or any of the amyl alcohols; and any of those alcohols may be used with sodium or potassium hydroxide to effect the reaction.

Under the broad class of compounds produced by the above method there is a nar- 49 rower class which may be represented by the following general formula v 50 wherein R represents an 'alkyl group, R rep- Serial No. 384,7 96 of which this application resents a benzene residue capable of being sulphonated and X represents hydrogen or a sulphonic acid group. F v

' According to the present invention we have found that the compounds of the above men- W on O/ rected to processes of making the dyes which do not contain a sulphonic acid group in the anthraquinone nucleus. The present application is mainly directed to a complete process of making sulphonated 2-alkoxy derivatives of the starting compounds, which contain in the l-position the group -N-R wherein R represents a benzene residue; this com- .plete process being effected, as a two-step process if desired.

Our invention is illustrated but not limited by the following examples:

I Example 1 i 10 parts of l-amino-2-metl1oxy-4-anilidoanthraquinone are dissolved in 50 parts of sulphuric acid monohydrate and sulphonated by pouring the whole onto-ice and filtering off theprecipitate which separates out.

It is redissolved in dilute alkali, neutralized and salted out. The resultant product dyes wool in level reddish violet shades of excellent fastness to light and milling. In a similar ma'nner 1'-amino-2-methoXy 4-p=toluresultant sulphonic acids are believed to contain *asulphonic group attached to the a'nil ido or "p-toluido residue. The dye Obtained from the p-toluido. body appears to be'identical with the dye obtained according to E2 ample 3 of the co.-pending application Serial No. 884;,7 96 of even date herewith.

. ..Ewample2. f

10 parts of 1-aniino-L-toluidoanthraquinproduct-is filtered off, dried and sulphonated.

with 6 partsof ole'um at-20 C. The

' meltis' poured on to ice, the resultant precipitate filtered ofl, redissolved in "dilute alkali, neutralized and salted out. The disulphonate thus obtained is very soluble and dyes I wool bluish'viol'et. V

Ewample 3.Prepamtioa of J-amkino-Z-methomy-ri-anZidoaatkmqwinone one-2-sulphonic acid are boiled with 100 {used the following: H

parts of methyl alcohol and 20 parts of sodium methylate. Aftera short time the new compound is precipitated and is filtered off and washed with hot water. It forms a blue As an alternative method there may be 7 IO parts of 1amino-4-anilidoanthraquinone-2-sulphonic acid are boiled for four hourswith 200 parts of methyl alcohol and 60 parts of caustic soda liquor of 7 8 Tw.

I The product is worked'up as above.

obtained Example 1. v

' 10 parts of l'-'amino-2-sulpho-(-sulpho ptoluido) anthraquinone are refluxed with 50 parts of methyl alcohol and 9 parts or ca'ustic soda for four hours. The new dye-stuflf 55 is filtered ofl and washed with a 2 per cent salt brine. It dyes wool in level violet shades which are fast to light and milling. This body appears to be the same product as that Example 5 :10 parts of l-amino -tolui-doanthraquinone+2 8-'disulphonic acid are refluxed for -s-ixhours with -80 parts of methyl alcohol formula 7 and 35 parts of caustic soda liquor of 78 Tw. The product isfiltered OE and dried.

Ewample "6.1-am?la0-2-et7z.omy-4-tolaidoanv y 1O, parts of '1 Q amino- 4 toluidoanthraidoanthraqulnone may be sulphonated. The f .qu-inone' -2-sulphonic acid are boiled for 1 hour wlth .80 flparts ofethyl alcohol and 5 parts of causticso'da. Thecresultan't purple crystals of '1 amino-2-ethoXy-4-p toluidoanthraqu-inone are filtered oil, washed with ,hotlwater and dried. The solution in sulphuric acid is re'd;, b'ecoming fluorescent on on addition oftormaldehyde.

a One-Q-btotyZ other I 10 partsof '1--amino p toluidoanthraquinfor one half hour with 100 parts of normal butyl alcohol andlorparts of caustic soda. The amino-toluidoanthraquinorre butyl ether is obtained" in the form of violet crystals which are filtered off, washed and-- dried;

The corresponding anili-do derivative is obtained in a similar manner from 1-a1nino-4- anilidoanthraquinone-2-sulphonic acid. Both these new bases give red 'colourations in sul- Whatwe claim and desire to securebyLet- 1. In a process of manufacturing dye tuff having the probable formula j son:

the process which comprises reacting 124-.

diaminoanthraquinone having the. probable Ho s with ole'um.

2. As a new dye, the l fa-di-aminoanthraquinone body having the probable formula HOaS O I NH:

phuri'c acid changing as blue'orl addition or I fortnaldehyde. 10 parts of 1 amin0-4-anilidoanthraquln- 1 aka the said dye being a powder soluble in water and dyeing wool in bluish to violet shades,

the said dye being obtainable by reacting a '1: 4-diaminoanthraquinone having the prob able formula ms 0 NH: I

it a 0on1 N-OCH: g with oleum.

3. As new dyes, the lzl-diaminoanthraquinone body having the probable formula 1103s 0 NH:

o t NQM H0 8 P bllHa t) NQRE wherein R represents hydrogen or a methyl group and R represents hydrogen or a sulphonic acid group, the said dyes being powders soluble in water and dyeing wool in bluish to violet shades.

5. As new dyes the 1 l-diaminoanthraquinone bodies having the probable formula 1103s 0 NH:

wherein R represents'an alkyl group, R represents hydrogen or an alkyl group, the said dyes being powders soluble in water and dye- 5 ing wool in bluish to violet shades.

6. As new dyes, the 1: 4-diaminoanthraquinone bodies having the probable formula 11038 E NH: GE N R5 AI tom wherein R represents hydrogen or a methyl group.

7. As a new dye, the lz i-diaminoanthra- OCH:

quinone body having the probable formula H0 8 O N H:

the said dye being a powder soluble. in Water.

8. As new dyes, the l 4-diaminoanthraquinone bodies having the probable formula HOzS E NH:

E NQCH: I 1!! 0,11

wherein R represents an alkyl group.

In testimony whereof We afiix our signatures.

FRANK LODGE. 7 WILLIAM WYNDHAM TATUM.

CERTIFICATE OF CORRECTION.

Patent No. 1,881,751. October 11, 1932.

FRANK LODGE ET AL.

It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction as follows: Page 2, line 71, for "1- amieo-4-toluid0anthra-"read 1- amino -4-p-toluidoanthra and that the said Letters Patent should be read with this correction therein that the same may conform to the record of the case in the Patent Office.

Signed and sealed this 29th day of November, A. D. 1932.

M. J. Moore,

(Seal) Acting Commissioner of Patents. 

